Graft polymers of vinyl chloride on unsaturated olefinic elastomers and process for the preparation thereof

ABSTRACT

Impact resistant compositions comprising crude graft polymers of vinyl chloride on unsaturated olefinic elastomers, said elastomers being copolymers of ethylene, an Alpha -olefin and a diene or a polyene, are prepared by graft polymerizing vinyl chloride onto an olefinic elastomer. The graft polymerization is discontinued before 70% of the vinyl chloride has been polymerized.

United States Patent Severini et aI,

[ @fiWfiZO June 24, I975 GRAFT POLYMERS OF VINYL CIILURIDIE 0N UNSATURATED OLEFINIC ELASTOMERS AND PROCESS IFQtR TII'IE PREPARATION THEREOF Inventors: Febo Severini; Alberto Vallvassori,

both of Milan; Alberto Pagliari, Saronno, all of Italy Assignee: Montecatini Edison S.p.A., Milan,

Italy Filed: Sept. 25, 1972 Appl. No.: 292,159

Foreign Application Priority Data Sept. 23, 1971 Italy 28984/71 US. (In 260/878 R; 260/876; 260/889;

260/897 C Int. Ql. C08f 15/00; C(I8f 29/12 FieIoI of Search 260/878 R [56] References Cited UNITED STATES PATENTS 3.676.528 7/1972 Severini et al. 260/878 R FOREIGN PATENTS OR APPLICATIONS 1,054,062 1/1967 United Kingdom 260/878 R Primary Examiner-Joseph L. Schofer Assistant E.\'aminerA. Holler Attorney, Agent, or FirmI-Iubbell, Cohen and Stiefel Ill Claims, No Drawings GRAFT PULYMERS T VllNYlL CHLURTDE @N UNSATlURATED OLEFINTC ELASTQMERS ANTI) PRO CESS lFtOlR THE PREPARATMDN Tll-lllETtEUlF BACKGROUND OF THE INVENTION 1, Field of the lnvention The present invention relates to impact resistant compositions comprising novel crude graft polymers of vinylchloride on unsaturated olefinic elastomers, said elastomers being copolymers of ethylene with an oz-oletin and a cyclic or acyclic diene or polyene, and a method for their preparation.

2. Prior Art lmpact resistant materials based on crude products of vinyl chloride grafted onto olefinic elastomers are already known. These materials, although providing manufactured articles of high impact resistance and resistance to aging, have, however, the disadvantage of being difficult to process in the techniques normally used in the transformation of polyvinyl chloride into manufactured articles. Moreover, these materials lead to products having substantial surface unevenness which practically precludes the possibility of using such articles.

The poor processability (workability) of the known high impact materials is evidenced by their low flowability in the molten state (melt index).

For example, the crude graft products which may be prepared by means of the known processes, and containing from 8 to 10% by weight of total olefinic elastomer, never have melt index values higher than 1 (measurement carried out according to ASTM D 1238 at 185C, with a load of 23.5 kg).

The methods heretofore used for the preparation of the above mentioned impact resistant materials comprise graft polymerizing vinyl chloride in the presence of an unsaturated olefinic rubber, until almost complete conversion of the monomer has occurred.

One of these methods is, for example, described in our Ttalian Patent No. 698,014 in the name of the assignee hereof. The method comprises polymerizing vinyl chloride in the presence of the olefinic rubber dissolved in the monomer, until a particularly high conversion rate has been obtained, and, in any case, greater than 75% conversionv The crude products which are obtainable by the method described in said ltalian Patent consist of mixtures comprising the following fractions that are separatable by extraction with solvents:

a. vinyl chloride homopolymers,

b. unmodified olefinic rubber, and

c. a real graft copolymer of rubber and vinyl chloride (a copolymer lacking free rubber and vinyl chloride homopolymers).

ln these crude products the content of grafted polyvinyl chloride is particularly high, and is generally greater than 45 50% by weight with respect to the weight of the graft copolymer.

DESCRTPTlON OF THE lNVENTlON According to the present invention, it has now been found, quite unexpectedly, that is is possible to prepare impact resistant compositions comprising novel products of vinyl chloride grafted onto unsaturated olefinic elastomers, having excellent workability characteristics in the processes normally used for polyvinyl chloride, and which, at the same time, are capable of being manufactured into articles that. in addition to having impact resistance characteristics and resistance to aging both under natural and artificial conditions, are free of surface unevenness.

The impact resistant compositions of this invention comprise mixtures of the following components:

a. polyvinyl chloride homopolymer,

b. graft copolymers of vinyl chloride, and

c. unmodified unsaturated olefinic elastomer.

These products are characterized by the fact that the content of polyvinyl chloride present in the graft copolymer (b) is between 15 and 60% by weight and by the fact that the melt index of the compositions (measured according to ASTM D 1238 at 185C, with a load of 23.5 kg) is always greater than 1 for compositions containing from 5 15% of total rubber (unmodified olefinic elastomer -lelastomer present in the graft copolymer).

The content of polyvinyl chloride present in the graft copolymer (b) depends on the degree of unsaturation of the olefinic elastomer used for the grafting; and the polyvinyl chloride content increases as the unsaturation increases. The polyvinyl chloride content is between 15% and 45% by weight when the elastomers used for grafting are, e.g., ethylene-propylene-ethylidenenorbornene terpolymers containing 1 5% by weight of diene. The polyvinyl chloride content exceeds 45% and may be as high as 60% or more when the content of ethylidenenorbornene in the terpolymer amounts to 10% by weight.

The components of the impact residual products of the invention are in general present in the following proportions by weight:

vinyl chloride homopolymers {component (a)]: 30 9571 free rubber [component (c)]: 1 2071 graft copolymers [component (b)]: balance to make up The total rubber content (i.e.: free rubber plus modifled rubber) present in the compositions according to the invention, in general, is between 2 and 60% by weight.

The percentage of free rubber with respect to the total rubber content depends on the degree of unsaturation of the rubber. in the case of rubbers containing 10% by weight of units derived from the diene or polyene, it is between about 15 and 30%. 1n the case of rubbers containing 1 5% by weight of units derived from the diene or polyene, it is 20 40% by weight.

in actual practice, the impact resistant compositions best suited for being transformed into manufactured articles contain from about 5% to 15% by weight of total rubber.

The compositions according to the invention may be obtained directly by grafting vinyl chloride onto the unsaturated elastomer. Alternatively, and this technique may be more desirable because it leads to a greater yield of grafted rubber, the compositions may be prepared by diluting crude graft products having a total rubber content of between 25% and 60% with separately prepared polyvinyl chloride.

The composition of the impact resistant materials according to the invention may be determined by separation of the components. This is done by determining the content of rubber soluble in n-heptane (free rubber) (a) and the residue (b) after extraction with cyclohexane (free rubber -1- pure graft copolymer).

By subtracting the amount of (a) from the amount of (b), one obtains the amount of pure graft copolymer, and, knowing the vinyl chloride content of (b), it is possible to obtain the composition of the graft copolymer of 'vinyl chloride on the olefinic elastomer. v

The determinations are carried out in the following way: an exactly weighed quantity of the crude polymer is contacted with an excess of tetrahydrofuran for 12 hours at room temperature to obtain a dispersion which contains small quantities of gel.

This dispersion is poured and uniformly distributed on a fixed quantity of Celite K-535 (a diatomaceous earth produced by Johns-Manville Co.). The tetrahydrofuran is then completely evaporated at room temperature and under reduced pressure. The dry residue is then introduced onto a chromatographic column thermostatically stabilized at 60C. n-l-leptane is percolated through the column until all the free rubber has been extracted therefrom. The heptane extract is then collected in a tared flask and evaporated under reduced pressure, after which it is weighed.

An exactly weighed quantity of the crude polymer is treated for 24 hours at room temperature with an excess of cyclohexanone to dissolve the polyvinyl chloride homopolymer contained therein.

Then the whole mass is filtered on a calibrated Gooch filter and weighed after drying to constant weight. The residue, consisting of free rubber and graft copolymer, is then subjected to chlorine analysis to determine the percentage of vinyl chloride present therein. 1 r

The olefinic elastomers used in the preparation of th compositions of the invention are slightly unsaturated V copolymers of ethylene with'a-olefins and with one or more cyclic or acyclic conjugated 0r non-conjugated dienes. or polyenes.

Preferably, the elastomer consists of substantially amorphous terpolymers of .ethylene with propylene or butene-l and with a third monomer selected from the group consisting of: butadiene, a 6-alkylidenenorbornene, norbornadiene-2,5, a 2-alkylnorbornadiene-2,5, cyclooctadiene-l,5, tetrahydroindene and Smethyltetrahydroindene.

Particularly interesting results have been obtained with ethylene-propylene-6-ethylidenenorbornene, ethylene-propylene-S-methyl-tetrahydroindene and ethylene-propylene-l,4-hexadiene terpolymers as the olefinic elastomer.

The diene or polyene content of the copolymers is between 2 and 20% by weight. The a-olefin content, in particular propylene, is between about 20% and 60% by weight.

The molecular weight of the copolymers is generally between about 10,000 and 1,000,000.

The crude graft products of the invention are obtained by the graft polymerization of vinyl chloride in the presence of the unsaturated olefinic elastomer.

The preparation method comprises graftpolymerizing vinyl chloride in bulk, emulsion, suspen sion or solution, and interrupting the reaction when the conversion of the monomer is not higher than 70%.

From a practical viewpoint only, it is preferred that the vinyl chloride conversion be not less than 30%, so that the preferred range of conversion is from 30% to Clearly, the reaction time and the percentage of rubber in the crudeproduct will be determined in accordance with the desired composition of the crude product, and more precisely, in accordance with the quantity of rubber present in the starting mixture with the vinyl chloride.

Preferably, the reaction is continued until the conversion reaches a value between 30% and 55% when the vinyl chloride/rubber ratio is between 10:1 and 5:1 by weight, and'the rubber has a degree of unsaturation of from 3 to 6 double bonds per 1000 carbon atoms, corresponding to a diene content of 3 to 5% by weight when ;8c ethylidenenorbornene is used as the diene. 14

However, when starting from elastomer/vinyl chloride systems with a high elastomer concentration, for example, between 25% and 50%, it is possible to graft polymerize to a much higher degree of conversion than is possible with systems having a low elastomer concentration.

In practice, the preparation of the grafts according to the preferred method described above may be carried out according to the following procedures.

A stainless steel reactor, fitted with a stirrer and a sleeve for the circulation of a heating liquid is charged with the elastomer which has been cut up into pieces. After removal of the air from the reactor, there is introduced thereto the vinyl chloride monomer. The reaction mass is kept under stirring at a temperature between about 20C and 60C, for a period of about 0.5 to 5 hours to dissolve or swell the rubber. To the mass there are then admixed the suspending medium dissolved in water and the reaction initiator. The whole mass is then heated to the desired temperature and the reaction is interrupted when the conversion of the monomer has reached the desired value.

After elimination of the unreacted monomer, the crude reaction product is separated from the suspending liquid by centrifuging, washed and finally dried.

It is preferable, when starting from elastomer/monomer systems having a high concentration of elastomer and containing, for instance, from 20% to 50% of elastomer, to carry out the polymerization under the following conditions.

An aqueous solution of the suspending medium and the rubber in granulated form are placed into the reactor. After removing the air from the reactor, the monomer is added thereto and the mass is then kept under stirring at a temperature between about room temperature and C, for about 0.5 to 10 hours, to promote the swelling or dissolution of the elastomer.

To this mass the initiator is then admixed. The reactor is then heated to the desired temperature and the polymerization is permitted to proceed until the desired degree of conversion is achieved. Thereupon the reaction mass is cooled, and after the elimination of the monomer, the polymer is separated from the suspending liquid by centrifuging.

Among the initiators which may be used in the graft reaction there are included peroxidic compounds which are soluble in the monomer, such as alkali metal persulfates, hydrogen peroxide and percarbonates. Also, azo-compounds such as azo-bisisobutyronitrile, the dimethyl ester of a,a-azobutyric acid, the

a,a-azodinitrile of a,,B-dimethylvaleric acid, may be such as starch, alginates and synthetic materials, such as polyvinylpyrrolidone, polyvinyl alcohol, partially hydrolyzed polyvinyl acetate, aliphatic esters of polyethyleneglycols, etc.

At the end of the reaction, if it has been carried out in suspension, the crude product is discharged in the form of white pearls, which product, after drying and analysis is stabilized by means of the ingredients conventionally used in the processing of polyvinyl chloride, such as the barium and cadmium stearates and laurates sold by Argus Chemical Co. under the trade name Mark WSX, and then transformed into manufactured articles.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The following examples are given for the purpose o'fi further illustrating the present invention without the invention being limited thereto. In these examples the samples used for evaluation were made on pressed plates, using the material obtained by homogenization of the starting powder after the addition of 2% of a Ba-Cd stabilizer; 0.05% of an organic phosphite; 0.1% of an antioxidant and 0.5% of a lubricant of the stearic type.

The measurements were made according to the pro cedures set forth in the following ASTM tests:

Izod resilience (notch impact strength): ASTM D 256; Rockwell hardness: ASTM D 785; and Melt index ASTM D 1238 (at 185C, under a 23.5

kg. load). In the Examples, various abbreviations appear. These abbreviations have the following meanings:

AIBN azo-bis-isobutyronitrile ENB ethylidenenorbornene MTHI methyltetrahydroindene M1 melt index VC vinyl chloride CH cyclohexanone PVC polyvinyl chloride TDM t-dodecylmercaptan VCD vinylidene chloride HD hexadiene-l,4.

EXAMPLE 1 Into a 2 liter stainless steel autoclave, 45 g of an ethylene-propylene-ENB terpolymer, consisting of 58.4% ethylene, 38% propylene and 3.6% ENB; and having a Mooney viscosity ML( 1+4) 100C 62, were introduced.

After removing the air from the autoclave, 500 g of VC were added thereto. After complete dissolution of the terpolymer in the monomer, 3 g of polyvinyl alcohol dissolved in 770 g of water, and 0.64 gram of AIBN were charged to the autoclave. This mixture was then heated to 65C and maintained at this temperature for 12 hours. Thereby, there were obtained 512 g of a product containing 8.8% of terpolymer. This product was stabilized with a Ba-Cd stabilizer, was then homogenized in a cylinder mixer. The sheet obtained thereby was compression molded, and the mechanical properties of the product were evaluated. The data are recorded in Table I.

EXAMPLE 2 The procedure used in Example 1 was followed, ex-

cept that the reaction was interrupted when about 50% of the monomer had been converted. As a result there were obtained 300 grams of a material containing 15% of terpolymer. The material was diluted to a final rubber content of 9% with PVC having a constant K according to Eikentscher of 60 (equal to that of the homopolymer which was formed during the reaction) and was then treated as in Example 1. The results are recorded in Table I.

EXAMPLE 3 Into a 2 liter autoclave 24 g of the terpolymer used in Example 1 and 500 g of vinyl chloride were charged. After the terpolymer had completely dissolved in the monomer, 3 g of polyvinyl alcohol dissolved in 770 g of water and 0.64 g of AIBN were charged into the autoclave.

This mixture was then heated to 65C and the reaction was interrupted as soon as the conversion of the monomer had reached about 50%. Thereby, there were obtained 264 g ofa product containing 9.1% of terpolymer. The product was then processed as in Example 1, and the obtained results are recorded in Table I.

EXAMPLE 4 Into a 2 liter autoclave grams of the terpolymer used in Example 1 and 500 g of vinyl chloride were charged. After the terpolymer had completely dissolved in the monomer, 3 g of polyvinyl alcohol dissolved in 770 g of water and 0.64 g of AIBN were charged into the autoclave.

This mixture was then heated to 65C and the reaction was interrupted as soon as the conversion of the monomer had reached about 50%.

Thereby, there were obtained 363 g ofa product containing 22% of terpolymer. The product was then processed as in Example 2 and the obtained results are recorded in Table I.

EXAMPLE 5 The same procedures as in Example 1 were followed, except that a terpolymer consisting of 51.5% ethylene, 39% propylene and 9.5% ENE and having a Mooney viscosity ML 1+4) C 72 was used. There were obtained 475 grams of a material containing 9.5% of terpolymer, which was processed as in Example 1. The results are recorded in Table I.

EXAMPLE 6 In a 2 liter autoclave, the procedure of Example 2 was repeated, except that the terpolymer of Example 5 was used. There were obtained 262 g of a material containing 17.2% of terpolymer, which was processed as in Example 2. The results are recorded in Table 1.

EXAMPLE 7 A 2 liter autoclave was charged with 45 g of a terpolymer consisting of:

56.6% ethylene, 40% propylene and 3.4% MTI-II; and having a Mooney viscosity ML (1+4') 100C 96.

Air was removed from the autoclave and 500 g of vinyl chloride were added. After complete dissolution of the terpolymer in the monomer, 3 g of polyvinyl alcohol dissolved in 770 g of deionized and boiled water and 0.64 g of AIBN were charged into the autoclave.

This mixture was then heated to 65C and the reaction was stopped when the conversion of the monomer had reached about 50%.

There were obtained 296 g of a material containing 15.2% of terpolymer, which was processed as in Example 2. The following results were observed: Izod resilience at 23C =71; Ml 3.

EXAMPLE 8 Example 7 was repeated, except that the terpolymer had the following composition: 56.7% ethylene, 40% propylene and 3.3% HD; with a Mooney viscosity ML (1+4) 100C 52.

There were obtained 292 g of a material containing 15.4% of terpolymer,'which was processed as in Example 2. The following results were observed: Izod resilience at 23C 65; M1 2.

EXAMPLE 9 A 2 liter stainless steel autoclave was charged with 3 g of polyvinyl alcohol dissolved in 740 g of deionized and boiled water and 180 g of a terpolymer consisting of 58.4% ethylene, 38% propylene and 3.6% ENB and having a Mooney viscosity ML (1+4) 100C 62.

After removal of the air from the autoclave, 500 g of vinyl chloride monomer were added thereto. This mixture was then stirred for 4 hours at 50C and thereafter,

. 0.64 g of AIBN dispersed in 210 g of water was added thereto. The whole mass was then heated at 65C and maintained at that temperature until the conversion of the VC had reached about 33%. There were obtained 355 g of a product containing 50.7% of terpolymer.

The thus obtained product was diluted to a terpolymer content of 9% with a PVC having a Fikentscher K index equal to that of the homopolymerthat had formed in the course of the reaction. The diluted product was then homogenized and compression molded as described in Example 1.

The results of the analysis of the composition of the crude reaction products and the values of the mechanical properties of the material are summarized in Table [1.

EXAMPLE 10 Example 9 was repeated, except that the reaction was permitted to proceed until the conversion of the VC had reached about 70%. Thus, there were. obtained 486 g of a material containing 37% of terpolymer. This material, diluted to a final rubber content of 9% was homogenized and compression molded as in Example 1, and showed the characteristics recorded in Table 11.

EXAMPLE 1 1 Example 9 was repeated except that the terpolymer consisted of 51.5% ethylene, 39% propylene and 9.5%

EXAMPLE 12 Example 11 was repeated, except that the reaction was interrupted when the conversion of the VC reached about There were obtained 439 g of a material that contained 41% of terpolymer.

The material, diluted to a total rubber content of 9%, homogenized and compression molded as described in Example 1, showed the characteristics reported in Table 11.

TABLE I Example Conver- Total Free Free CH resi- 7:- PVC on graft 7: VC in 7: VC in No. sion of rubber on rubber on rubber on due on cru crude proon crude CH resithe VC crude crude total de product duct l product(2) due graft product product rubber I 93.2 8.8 2.4 27.3 17.0 83 14.6 44.1 51.4 2 51.0 15.0 5.7 38.0 21.0 79 15.3 25.6 35.2 3 48.6 9.0 3.5 38.9 13.3 86.7 9.8 32.8 44.5 4 56.6 22.0 8.5 38.6 28.2 71.8 19.7 27.0 38.6 5 85.7 9.5 3 31.4 24.6 75.4 21.6 60.0 68.3 6 43.4 17.2 5.9 34.4 27.3 72.7 21.4 41.8 53.4

11nd 23C Ml Mechanical Properties (kg.cm/cm) (g! 10 min.) Rockwell Hardness 1 86* 0.1 64 L 2 88* 4 64 L 3 72* 2 96 R 4 65* 7 98 R 5 71* 0.2 60 L 6 66* 20 60 L The test pieces partially hrokc. (1 Values calculated as completion to 100 of the cyclohexanonc residue. (2) Values calculated as the difference between cyclohcxanonc residue and free rubber.

TABLE 11 Example Converof total 7: of free 70 of CH of PVC of graft 7: VC in 71 VC in lzod M1 N0. sion of rubber on rubber on residue on crude on crude CH the at 23C (gl 10 VC crude total on crude product product residue graft (kg.cm/ min.)

product rubber product 1) 2) 1, cm) 9 33.2 50.7 58.2 59.3 40.7 29.8 19.8 39.4 10 68.6 37.0 30.5 49.4 50.6 38.1 35.0 45.3 72" 23.5

- TABLE 11 Continued Example /1 Conver- "/1 of total 71 of free "/1 of CH "/1 of PVC 71 of graft '71 VC in /1 VC in Izod M1 N0. sion of rubber on rubber on residue on crude on crude CH the at 23C (g/lO VC crude total on crude product product residue graft (l g.cm/ min.)

product rubher product 1 (2) cm) The test pieces partially hrokc. (1) Values calculatc as completion to 100 of cyclohcxunone residue.

(2) Values calculated as the difference between cyclohcxanonc residue and free rubber.

Variations and modifications can, of course, be made without departing from the spirit and scope of the invention.

Having thus described our invention, what we desire to secure by Letters Patent and hereby claim is:

1. An impact resistant polymeric composition comprising a mixture of the following components:

a. a vinyl chloride homopolymer, b. a graft copolymer of 15-60% by weight of vinyl chloride on an olefinic elastomer which comprises a copolymer of ethylene, an a-olefin and a minor amount of a cyclic or acyclic diene or polyene, and c. an unmodified olefinic elastomer; said composition having a melt index (determined according to ASTM D 1238 at 185C with a load of 23.5 kg) greater than 1 when the composition contains from 5 to 15% of total rubber, which is defined as the sum of the amounts of olefinic elastomer contained in components (b) and (c).

2. A composition according to claim 1, wherein component (a) comprises 30-95%, component (0) comprises l-% and component (b) makes up the balance; provided, however, that the total rubber content is between 2 and 60% by weight.

3. A composition according to claim 1, consisting of a crude graft product of vinyl chloride grafted onto an olefinic elastomer.

4. A composition according to claim 2, consisting of a crude graft product of vinyl chloride grafted onto an olefinic elastomer.

5. A composition according to claim 3, wherein the v is not higher than crude graft product contains from 25% to 60% by weight of total rubber.

6. A compositions according to claim 4, wherein the crude graft product contains from 25% to 60% by weight of total rubber.

7. A composition according to claim 1, wherein the olefinic elastomer is a terpolymer of ethylene, propylene and at least one cyclic or acyclic diene or polyene.

8. A composition according to claim 7, wherein the olefinic elastomer is a terpolymer of ethylene, propylene and at least one member selected from the group consisting of butadiene, a 6-alkylidenenorbornene, norbornadiene-2,5, a 2-alkylnorbornadiene-2,5, cyclooctadiene-l ,5, tetrahydroindene and S-methyltetrahydroindene.

9. A process for preparing a composition according to claim 11, comprising graft polymerizing vinyl chloride onto an olefinic elastomer, wherein the polymerization is discontinued when the vinyl chloride conversion is not higher than 70%.

10. A process according to claim 9 comprising graft polymerizing vinyl chloride onto an olefinic elastomer, wherein the polymerization is discontinued when the vinyl chloride conversion is comprised between 30% and 70%.

11. A process for preparing a composition according to claim 5, comprising graft polymerizing an olefinic elastomer/vinyl chloride system containing from 20% to 65% of olefinic elastomer, wherein the polymerization is discontinued when the vinyl chloride conversion mg UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION 201-52 Patent No. 3 891, 720 Dated July 7 1975 lnventor(s) FEBO SEVERINI et al It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

Title page, left side, in the Priority Date: "28984/71" should read 28984-A/7l Column 1, line 40: "our Italian" should read Italian line 63: "that is is" should read that it iS Column 2, lines l-2: "having impact" should read having high impact line 31: "impact residual" should read impact resistant lines 67-68: "cyclohexane" should read cyclohexanone Column 3, lines 43-44: '5methyl-tetrahydroindene" should read S-methyl-tetrahydroindene Column 4, line ll: "when ;8c" should read when same line: "diene. 14" should read diene.

4 Column 10, line 15 "compositions" should read composition Signed and Sealed this twenty-third Day of Septemberl975 [SEAL] A rtesr:

RUTH C. MASON C. MARSHALL DANN :Hlmlmg Officer (mnmixxlmu'r nl'luu'ms and Trademarks" 

1. AN IMPACT RESISTANT POLYMERIC COMPOSITION COMPRISING A MIXTURE OF THE FOLLOWING COMPONENTS: A. A VINYL CHLORIDE HOMOPOLYMER, B. A GRAFT COPOLYMER OF 15-60% BY WEIGHT OF VINYL CHLORIDE ON AN OLEFINIC ELASTOMER WHICH COMPRISES A COPOLYMER OF ETHYLENE, AN A-OLEFIN AND A MINOR AMOUNT OF A CYCLIC OR ACYCLIC DIENE OR POLYENE, AND C. AN UNMODIFIED OLEFINIC ELASTOMER, SAID COMPOSITION HAVING A MELT INDEX (DETERMINED ACCORDING TO ASTMD 1238 AT 185*C WITH A LOAD OF 23.5KG) GREATER THAN 1 WHEN THE COMPOSITION CONTAINS FROM 5 TO 15% OF TOTAL RUBBER, WHICH IS DEFINED AS THE SUM OF THE AMOUNTS OF OLEFINIC ELASTOMER CONTAINED IN COMPONENTS (B) AND (C).
 2. A composition according to claim 1, wherein component (a) comprises 30-95%, component (c) comprises 1-20% and component (b) makes up the balance; provided, however, that the total rubber content is between 2 and 60% by weight.
 3. A composition according to claim 1, consisting of a crude graft product of vinyl Chloride grafted onto an olefinic elastomer.
 4. A composition according to claim 2, consisting of a crude graft product of vinyl chloride grafted onto an olefinic elastomer.
 5. A composition according to claim 3, wherein the crude graft product contains from 25% to 60% by weight of total rubber.
 6. A compositions according to claim 4, wherein the crude graft product contains from 25% to 60% by weight of total rubber.
 7. A composition according to claim 1, wherein the olefinic elastomer is a terpolymer of ethylene, propylene and at least one cyclic or acyclic diene or polyene.
 8. A composition according to claim 7, wherein the olefinic elastomer is a terpolymer of ethylene, propylene and at least one member selected from the group consisting of butadiene, a 6-alkylidenenorbornene, norbornadiene-2,5, a 2-alkylnorbornadiene-2,5, cyclooctadiene-1,5, tetrahydroindene and 5-methyl-tetrahydroindene.
 9. A process for preparing a composition according to claim 1, comprising graft polymerizing vinyl chloride onto an olefinic elastomer, wherein the polymerization is discontinued when the vinyl chloride conversion is not higher than 70%.
 10. A process according to claim 9, comprising graft polymerizing vinyl chloride onto an olefinic elastomer, wherein the polymerization is discontinued when the vinyl chloride conversion is comprised between 30% and 70%.
 11. A process for preparing a composition according to claim 5, comprising graft polymerizing an olefinic elastomer/vinyl chloride system containing from 20% to 65% of olefinic elastomer, wherein the polymerization is discontinued when the vinyl chloride conversion is not higher than 70%. 